全文获取类型
收费全文 | 247篇 |
免费 | 11篇 |
专业分类
化学 | 204篇 |
晶体学 | 6篇 |
力学 | 3篇 |
数学 | 9篇 |
物理学 | 36篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 1篇 |
2017年 | 5篇 |
2016年 | 5篇 |
2015年 | 10篇 |
2014年 | 5篇 |
2013年 | 15篇 |
2012年 | 26篇 |
2011年 | 19篇 |
2010年 | 7篇 |
2009年 | 8篇 |
2008年 | 27篇 |
2007年 | 13篇 |
2006年 | 11篇 |
2005年 | 20篇 |
2004年 | 10篇 |
2003年 | 4篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1996年 | 3篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1970年 | 2篇 |
1939年 | 1篇 |
排序方式: 共有258条查询结果,搜索用时 31 毫秒
1.
Keigo Fugami Takashi Nishikata Masayuki Kameyama 《Journal of organometallic chemistry》2003,687(2):567-569
Palladium-catalyzed reaction between 1-alkenyltin trichlorides and norbornene resulted in stereoselective formation of 3-alkylidenepentacyclo[9.2.1.5,81.1,110.2,1004,9]pentadecane instead of an expected simple alkenylstannylation product. Generation of trichlorostannane and its decomposition product, tin(II) chloride, was confirmed by trapping it with methyl propiolate and norbornene and analysis of the reaction by 119Sn NMR, respectively. 相似文献
2.
P.M.?Kosaka Y.?Kawano M.C.?Salvadori D.F.S.?PetriEmail author 《Cellulose (London, England)》2005,12(4):351-359
The adsorption of cellulose acetate (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from solutions
prepared in acetone onto silicon wafers led to ultrathin films, which were characterized by ellipsometry, atomic force microscopy
(AFM) and contact angle measurements. The polysaccharides films were characterized in the air just after their formation and
after annealing at temperatures higher than their glass transition temperature or melt temperature. The films thickness close
to 2 nm and surface roughness did not vary significantly upon annealing. AFM images revealed the presence of small clumps
dispersed on a homogeneous layer, which covered completely the Si wafers. Such topographic details were also observed after
annealing. However, upon annealing the films surfaces changed from hydrophilic to hydrophobic, evidencing molecular re-orientation
at the solid–air interface. The adhesion of bovine serum albumin (BSA) and lipase onto the cellulose esters films was quantified
in order to evaluate the possibility of applying such films as selective support for biomolecules. 相似文献
3.
Mitsutaka Saito Hideo Tada Yujiro Kosaka 《Journal of polymer science. Part A, Polymer chemistry》1970,8(9):2555-2562
Ethylene–vinyl acetate copolymers contain two kinds of side chains: acetoxy branches originating from incorporated vinyl acetate and alkyl branches. The alkyl branching was determined by infrared analysis after converting the ethylene–vinyl acetate copolymer to a hydrocarbon polymer by three steps: hydrolysis, iodation with hydriodic acid containing red phosphorus, and reductive hydrogenation with lithium aluminum hydride. It was found that physical properties such as stiffness were dependent both on the degree of alkyl chain branching and on vinyl acetate content. 相似文献
4.
Motozaki T Sawamura K Suzuki A Yoshida K Ueki T Ohara A Munakata R Takao K Tadano K 《Organic letters》2005,7(11):2265-2267
[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1. 相似文献
5.
Stereoselective polymerization of racemic lactide (rac-LA) was examined using Al-achiral ligand complexes. By introduction of substituents in aromatic rings of Schiff base ligands, a higher selectivity was obtained without any chiral auxiliaries in the catalyst via a chain-end control mechanism. The T(m) values (T(m) 170-192 degrees C) were comparable to or higher than that of homochiral polymer, poly(L-LA) (T(m) 162 degrees C), and a thermally more stable polylactide than poly(L-LA) was prepared from rac-LA. 相似文献
6.
7.
Masahiko Okada Keigo Aoi Wataru Mizuno Shinji Ito 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1135-1140
New polyesters 6a–6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates ( 5a and 5b ) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate ( 5c ) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 104. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a . Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b , and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc. 相似文献
8.
Yozo Kosaka Toshiyuki Uryu 《Journal of polymer science. Part A, Polymer chemistry》1995,33(13):2221-2232
Side-chain liquid-crystalline copolymers and polymer blends containing an electron-donating (carbazolylmethylene)aniline group and electron-accepting nitrophenyl groups with various central linking groups between aromatic groups in the mesogenic units, i.e., N?CH, CH?CH, N?N, and COO, were prepared to examine effects of the mesogenic structure on thermal behaviours. The most remarkable effects of the central linking group on the thermal properties and the miscibility were observed for the polymer blends. The 1:1 miscible polymer blends were prepared from the electron-donating polymer containing (carbazolylmethylene)aniline group (PM6Cz) and the electron-accepting polymers with similar central linking groups, i.e., N?CH, CH?CH, and N?N. For example, the 1: 1 polymer blend of PM6Cz and the electron-accepting polymer containing the nitrostilbene group induced a smectic phase from 73 to 207°C. This isotropic temperature was 46°C higher than the calculated value (161°C) based on the composition without the electron donor-acceptor interaction. On the other hand, the 1: 1 polymer blend of PM6Cz and the electron-accepting polymer containing the nitrophenylbenzoate group showed phase separation. Thus, the remarkable thermal stability and the miscibility of the polymer blends containing the electron donor and acceptor groups might be caused by planar structures between the mesogenic side groups which have similar central linking groups through the electron donor-acceptor interaction. A similar tendency was seen for copolymers and binary mixtures of both low-molecular-weight compounds containing the same mesogenic groups. © 1995 John Wiley & Sons, Inc. 相似文献
9.
Bunai K Ariga M Inoue T Nozaki M Ogane S Kakeshita H Nemoto T Nakanishi H Yamane K 《Electrophoresis》2004,25(1):141-155
We analyzed ABC transporter solute-binding proteins (SBPs) of the Bacillus subtilis membrane using a proteomic approach. We prepared a washed cell membrane fraction that was insoluble in 134 mM nondetergent sulfobetaine and then extracted proteins using mixtures of detergents in a stepwise manner. The membrane proteins were resolved by three two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) or two one-dimensional (1-D) PAGE procedures, electroblotted, and digested in the presence of 5% or 80% acetonitrile. Thereafter, matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF MS) identified 637 proteins corresponding to 15.9% of the total cellular proteins. We predicted that among these, 256 were membrane proteins, 101 were lipoproteins or secretory proteins and 280 were soluble proteins containing peripheral proteins that function in both the cytoplasm and the cell membrane such as SecA and FtsY. Among the 637 proteins, we identified 30 SBPs among 38 importers predicted by a bioinformatic search of the genome. We confirmed expression of the genes for the 30 SBPs using DNA microarray analysis. We compared the 2-D gel separation profiles of submembrane fractions solubilized by 1% n-dodecyl-beta-D-maltoside from cells cultured on Luria Bertani (LB), S7, and S7 medium without glutamate as well as DNA microarray data on LB and S7. The results suggested that YcdH, YtmK and YurO are binding proteins for Mn(++), glutamate and glucose, respectively, and that YqiX and YxeM are binding proteins for amino acids (tryptophan in S7 medium). 相似文献
10.
Kosaka T Yoneyama-Takazawa T Kubota K Matsuoka T Sato I Sasaki T Tanaka Y 《Journal of mass spectrometry : JMS》2003,38(12):1281-1287
We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging. 相似文献